CN114853003A - Preparation method of waste plastic blended and co-thermally converted low-rank coal-based hard carbon material - Google Patents
Preparation method of waste plastic blended and co-thermally converted low-rank coal-based hard carbon material Download PDFInfo
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- CN114853003A CN114853003A CN202210650351.1A CN202210650351A CN114853003A CN 114853003 A CN114853003 A CN 114853003A CN 202210650351 A CN202210650351 A CN 202210650351A CN 114853003 A CN114853003 A CN 114853003A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 124
- 239000003245 coal Substances 0.000 title claims abstract description 115
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 113
- 229920003023 plastic Polymers 0.000 title claims abstract description 64
- 239000004033 plastic Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 62
- 238000005406 washing Methods 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000003763 carbonization Methods 0.000 claims abstract description 37
- 238000005554 pickling Methods 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000010000 carbonizing Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 238000012216 screening Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000009656 pre-carbonization Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 57
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- 239000004698 Polyethylene Substances 0.000 claims description 33
- 229920000573 polyethylene Polymers 0.000 claims description 33
- -1 polyethylene Polymers 0.000 claims description 30
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 24
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000002802 bituminous coal Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 24
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 23
- 239000011734 sodium Substances 0.000 abstract description 23
- 229910052708 sodium Inorganic materials 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 17
- 239000012300 argon atmosphere Substances 0.000 description 16
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 15
- 238000010998 test method Methods 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 12
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- 238000009826 distribution Methods 0.000 description 11
- 239000011229 interlayer Substances 0.000 description 10
- 238000007599 discharging Methods 0.000 description 7
- 239000013081 microcrystal Substances 0.000 description 7
- 241000446313 Lamella Species 0.000 description 6
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 229920000052 poly(p-xylylene) Polymers 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000003476 subbituminous coal Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 241001441723 Takifugu Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a waste plastic blending co-thermal conversion low-rank coal-based hard carbon material, which comprises the following steps: step one, raw material pretreatment: crushing and screening raw coal to obtain raw coal powder with a target particle size; step two, acid washing and deashing: firstly, carrying out acid pickling and deashing treatment on raw coal powder by using hydrochloric acid, water, hydrofluoric acid and water in sequence, and then fully drying; step three, mixing and carbonizing waste plastics: uniformly mixing the acid-washed and dried raw coal powder with waste plastics, and pre-carbonizing the mixture in inert gas to obtain a pre-carbonized product; step four, high-temperature carbonization: and grinding the pre-carbonized product uniformly, and then carrying out secondary carbonization in inert gas to obtain the low-order coal-based hard carbon material. The invention only adds plastic doping and pre-carbonization processes in the traditional direct carbonization process, has simple preparation method, convenient treatment and low cost, can effectively improve the sodium storage/capacity of the low-order coal-based hard carbon material, and is beneficial to commercial application.
Description
Technical Field
The invention relates to a preparation method of an electrode material, in particular to a preparation method of a low-order coal-based hard carbon anode material based on plastic blending and co-thermal conversion for a battery anode.
Background
Lithium ion batteries with the proportion of machines in the global electrochemical energy storage being over 80 percent face the problems that the energy storage requirement for rapid expansion is difficult to meet due to small lithium resource reserves, uneven distribution and the like, and the price of battery-grade lithium raw materials is increased year by year due to large mineral difference; sodium is similar to lithium in family and physicochemical properties, is tens of times more abundant than lithium and is sourced from the sea, and is considered as one of important substitutes of lithium ion batteries. The carbon negative electrode material is faced with the problems of low mass specific capacity, low density and other application performances, and is a key ring for improving the performance of the sodium ion battery.
Coal is used as a natural carbon source with the most abundant reserves and the lowest price in the nature, and a macromolecular structure with initial aromatization provides a structural basis for the functional design of a carbon material, and has great potential for developing hard carbon, soft carbon, graphite and even graphene. The high-rank coal such as anthracite has a larger aromatic element structure, so that the prepared carbon material has smaller lattice spacing and larger lamella size, is not beneficial to further improving the sodium/potassium ion embedding storage capacity and the rate capability, and the construction of the short-range ordered graphite-like crystal structure is the key point of quick and high-density sodium ion embedding storage. Low-rank coals such as lignite, subbituminous coal and the like have younger coal molecular structures, aromatic rings of the low-rank coals are 1-4 rings, and high-disorder hard carbon materials are easily formed in the thermal conversion process. The graphite-like crystal forms which are ordered in short distance and are in disordered arrangement have the problems of poor conductivity and hindered ion transportation when being used for sodium/potassium ion storage and transportation, thereby causing low specific capacity or poor large-current discharge capacity.
When the aromatic hydrocarbon compound is heated to 350-500 ℃ in an inert atmosphere for liquid-phase carbonization, a series of chemical reactions such as pyrolysis, cyclization, polycondensation and aromatization occur in molecules, the degree of polymerization reaction is continuously improved, the thermal motion of the molecules is intensified, the frequency of collision among the molecules is increased, association is generated among the molecules in the vertical plane direction due to van der waals force and molecular dipole moment, short-range arrangement and aggregation accumulation are formed, and the development of microcrystals in the subsequent high-temperature carbonization stage can be deeply influenced by the generated mobile phase and conversion behavior.
A large amount of waste plastics are discarded in the natural environment, so that the problems of 'micro-plastic' pollution and the like are caused, and at present, part of students prepare the hard carbon cathode material of the sodium ion battery by simply carbonizing the waste plastics in one step, but the problem of poor rate capability under high current density exists. The plastic is a thermoplastic polymer, is molten at a lower temperature, has a high contact ratio between a pyrolysis weight loss interval and a low-rank coal pyrolysis temperature area, and has the possibility of cooperative transformation. By utilizing the characteristic of the waste plastic, the preparation of microcrystals and pores in the co-thermal conversion process with coal is expected to be realized, and further the basic electrochemical characteristic of the low-order coal-based hard carbon material in the application of sodium storage is improved.
Disclosure of Invention
The invention provides a preparation method of a low-rank coal-based hard carbon material through blending and co-thermal conversion of waste plastics, aiming at the technical bottleneck that the sodium storage capacity of the traditional direct carbonization low-rank coal-based hard carbon material is poor and aiming at increasing the graphite microcrystal interlayer spacing in the high-rank coal high-temperature carbonization process. The method mixes the waste plastic with the coal powder according to a certain proportion, regulates and controls the thermal conversion process of the coal, and develops the waste plastic into the sodium-carbon storage negative electrode material with high specific capacity and high large current discharge capacity. Specifically, low-rank coals such as lignite and subbituminous coal are used as main raw materials, a mobile phase is provided at a lower temperature (250-400 ℃) through waste plastic blending, the original organization rearrangement mode of aromatic lamella in the coal is changed, the orientation orderliness of the lamella is optimized, and meanwhile, a resonance stable free radical is introduced to be used as a nucleating agent to induce the thermal polycondensation process in the coal; and further gasifying the plastic residues fused among the pulverized coal at a higher temperature (400-700 ℃) to form micro-nano pores and optimize mass transfer channels of ions and solvent molecules.
The purpose of the invention is realized by the following technical scheme:
a preparation method of waste plastic blended and co-thermally converted low-rank coal-based hard carbon material is shown in figure 1 and comprises the following steps:
step one, raw material pretreatment:
crushing and screening raw coal to obtain raw coal powder with a target particle size, wherein:
considering the actual effect of the waste plastic doping pre-carbonization and secondary carbonization method on the regulation and control of the carbon material graphite microcrystal/pore structure, the raw coal is one or a mixture of lignite I, lignite II and bituminous coal;
in order to ensure the blending depth in the waste plastic pre-blending step and facilitate the carbon electrode manufacture after the carbonization step is finished, the target coal particle size is 120-400 meshes, and the particle size of the waste plastic can not exceed 3 mm;
step two, acid washing and deashing:
the method comprises the following steps of carrying out acid pickling and deashing treatment on raw coal powder by sequentially using hydrochloric acid, water, hydrofluoric acid and water, and then fully drying, wherein:
the concentration of the hydrochloric acid is 2-5M, the concentration of the hydrofluoric acid is 5-20 wt%, and the ratio of the volume of the acid to the mass of the raw coal powder is 5-20: 1;
the water is distilled water or deionized water with the resistivity not less than 10M omega cm, and the final effect of water washing is that the supernatant of the solution is neutral or weakly acidic;
step three, mixing and carbonizing waste plastics:
uniformly mixing the acid-washed and dried raw coal powder with waste plastics, and pre-carbonizing the mixture in inert gas to obtain a pre-carbonized product, wherein:
the mass ratio of the raw coal powder to the waste plastics is 1: 0.01-2;
the waste plastic is one or a mixture of Polyethylene (PE), polypropylene (PP), Polystyrene (PS) and polyethylene terephthalate (PET), is used for cooperating with coal in a co-carbonization process, and can be regulated into carbon microcrystal and a pore structure;
the inert gas is one or more of nitrogen and argon, and the flow rate is 100-150 mL/min;
the pre-carbonization conditions were as follows: heating to 450-700 ℃ according to a heating rate of 2-50 ℃/min (preferably, the heating rate is 10-15 ℃/min), and preserving heat for 1-2 h;
step four, high-temperature carbonization:
grinding the pre-carbonization product uniformly, and then carrying out secondary carbonization in inert gas to obtain the low-order coal-based hard carbon material, wherein:
the inert gas is one or more of nitrogen and argon;
the conditions of the secondary carbonization are as follows: heating to 1000-1400 ℃ according to the heating rate of 2-5 ℃/min, and preserving heat for 1-2 h.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the carbon microcrystal and pore structure is regulated and controlled by co-carbonizing the doped waste plastic and the coal, the interlayer spacing of the graphite microcrystal is improved, the specific capacity is greatly improved compared with that of a carbonized material without doped plastic, and the first coulombic efficiency is still kept at 75-85%.
(2) The raw materials used in the invention are waste plastics and coal (especially low-rank coal), have wide sources and low price, and are beneficial to realizing the resource treatment of the waste plastics and the high-valued utilization of the low-rank coal.
(3) The invention only adds plastic doping and pre-carbonization processes in the traditional direct carbonization process, has simple preparation method, convenient treatment and low cost, and can effectively improve the sodium storage/capacity (about 50mAh g) of the low-order coal-based hard carbon material -1 ) And is beneficial to commercial application.
Drawings
FIG. 1 is a flow chart illustrating the preparation of a waste plastic blending co-thermally converted low-rank coal-based hard carbon material according to the present invention;
FIG. 2 is an XRD spectrum of a 1:2 (plastic: coal) blended Polyethylene (PE)450 ℃ pre-carbonized 1200 ℃ post-carbonized brown coal-based hard carbon material as described in example 5.
FIG. 3 is an SEM image of a 1:2 (plastic: coal) blended Polyethylene (PE)450 ℃ pre-carbonized 1200 ℃ post-carbonized brown coal-based hard carbon material as described in example 5.
FIG. 4 is a graph showing the charging and discharging curves of the brown coal-based hard carbon material pre-carbonized at 450 ℃ and secondarily carbonized at 1200 ℃ in a 1:2 (plastic: coal) blend Polyethylene (PE) as described in example 5.
FIG. 5 is a graph of the rate capability of a 1:2 (plastic: coal) blended Polyethylene (PE) lignite-based hard carbon material pre-carbonized at 450 ℃ and post-carbonized at 1200 ℃ as described in example 5.
FIG. 6 is an XRD spectrum of a 1:1 (plastic: coal) blended Polyethylene (PE) lignite-based hard carbon material pre-carbonized at 450 ℃ and post-carbonized at 1400 ℃ as described in example 6.
FIG. 7 is a graph of the pore size distribution of a 1:1 (plastic: coal) blended Polyethylene (PE) lignite-based hard carbon material pre-carbonized at 450 ℃ and post-carbonized at 1400 ℃ as described in example 6.
FIG. 8 is a graph of rate capability of a 1:1 (plastic: coal) blended Polyethylene (PE) lignite-based hard carbon material pre-carbonized at 450 ℃ and post-carbonized at 1400 ℃ as described in example 6.
FIG. 9 is a graph showing the charging and discharging curves of the brown coal-based hard carbon material pre-carbonized at 450 ℃ and secondarily carbonized at 1400 ℃ in a 1:1 (plastic: coal) blend Polyethylene (PE) process described in example 6.
Figure 10 is an XRD spectrum of a 450 ℃ pre-carbonized, 1200 ℃ secondary carbonized processed brown coal based hard carbon material as described in example 7.
Fig. 11 is an SEM image of a 450 ℃ pre-carbonized, 1200 ℃ secondary carbonized processed brown coal-based hard carbon material described in example 7.
FIG. 12 is a graph showing the charge and discharge curves of the brown coal-based hard carbon material pre-carbonized at 450 ℃ and secondarily carbonized at 1200 ℃ as described in example 7.
Fig. 13 is a graph of rate capability of the brown coal-based hard carbon material pre-carbonized at 450 ℃ and post-carbonized at 1200 ℃ as described in example 7.
Figure 14 is an XRD spectrum of a 450 ℃ pre-carbonized, 1400 ℃ secondary carbonized processed brown coal based hard carbon material as described in example 8.
FIG. 15 is a graph of the pore size distribution of a 450 ℃ pre-carbonized 1400 ℃ post-carbonized brown coal-based hard carbon material described in example 8.
Fig. 16 is a graph of rate capability of the brown coal-based hard carbon material pre-carbonized at 450 ℃ and post-carbonized at 1400 ℃ as described in example 8.
FIG. 17 is a graph showing the charging and discharging curves of the brown coal-based hard carbon material pre-carbonized at 450 ℃ and secondarily carbonized at 1400 ℃ as described in example 8.
FIG. 18 is an XRD spectrum of a 1:2 (plastic: coal) blended polyethylene terephthalate (PET)700 ℃ pre-carbonized 1200 ℃ post-carbonized brown coal-based hard carbon material as described in example 10.
FIG. 19 is an SEM image of a 1:2 (plastic: coal) blended polyethylene terephthalate (PET)700 ℃ pre-carbonized 1200 ℃ double carbonized brown coal-based hard carbon material as described in example 10.
FIG. 20 is a graph of rate capability of a 1:2 (plastic: coal) blended polyethylene terephthalate (PET) pre-carbonized at 700 ℃ and post-carbonized at 1200 ℃ brown coal-based hard carbon material as described in example 10.
FIG. 21 is a graph showing the charging and discharging curves of the brown coal-based hard carbon material pre-carbonized at 700 ℃ and post-carbonized at 1200 ℃ in a 1:2 (plastic: coal) blend with polyethylene terephthalate (PET) as described in example 10.
FIG. 22 is an XRD spectrum of a 1:2 (plastic: coal) blended polyethylene terephthalate (PET) pre-carbonized at 700 ℃ and post-carbonized at 1400 ℃ brown coal-based hard carbon material treated in example 11.
FIG. 23 is a graph of the pore size distribution of a 1:2 (plastic: coal) blended polyethylene terephthalate (PET) pre-carbonized at 700 ℃ and post-carbonized at 1400 ℃ brown coal-based hard carbon material as described in example 11.
FIG. 24 is a graph of rate capability of brown coal-based hard carbon material treated by 1:2 (plastic: coal) blending polyethylene terephthalate (PET) pre-carbonization at 700 ℃ and secondary carbonization at 1400 ℃ as described in example 11.
FIG. 25 is a graph showing the charging and discharging curves of a 1:2 (plastic: coal) blended polyethylene terephthalate (PET) pre-carbonized at 700 ℃ and post-carbonized at 1400 ℃ brown coal-based hard carbon material as described in example 11.
FIG. 26 is a graph of rate capability of a brown coal-based hard carbon material pre-carbonized at 700 ℃ and post-carbonized at 1400 ℃ as described in example 14.
FIG. 27 is a graph showing the charging and discharging curves of the brown coal-based hard carbon material pre-carbonized at 700 ℃ and secondarily carbonized at 1400 ℃ as described in example 14.
Fig. 28 is a graph of rate capability of the brown coal-based hard carbon material pre-carbonized at 700 ℃ and post-carbonized at 1400 ℃ described in example 15.
FIG. 29 is a graph of the pore size distribution of a brown coal-based hard carbon material pre-carbonized at 700 ℃ and post-carbonized at 1400 ℃ as described in example 15.
Detailed Description
The technical solutions of the present invention are further described below with reference to the following examples, but the present invention is not limited thereto, and any modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Example 1:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, pre-blending and carbonizing: uniformly mixing the powder with Polyethylene (PE) according to a ratio of 1:1, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 1.5h to obtain a pre-carbonized sample.
Step three, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
Step four, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the hard carbon.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. Mixing a hard carbon material, a binder (polyvinylidene fluoride, PVDF) and a conductive agent (acetylene black) according to the weight ratio of 17: 3: 2, weighing the corresponding three materials, uniformly mixing the three materials in an agate mortar, then dropwise adding a dispersing agent (N-methylpyrrolidone, NMP) and fully stirring the mixture. And uniformly coating the uniformly stirred paste on a copper foil with the thickness of about 0.02mm, transferring the copper foil coated with the film into a vacuum drying oven, drying for 12 hours at the temperature of 80 ℃, and stamping the dried film into a circular pole piece by using a special die after a dispersing agent (N-methylpyrrolidone, NMP) in the copper foil is completely removed.
Assembling the punched electrode plate and sodium metal counter electrode into CR2032 button cell, separating positive electrode current collector with insulating spacer and positive and negative electrodes with separator, and dripping 180 μ L of NaClO 4 And (4) fully soaking the electrolyte. The whole battery assembling process is completed in an ultra-clean glove box filled with argon. And after the battery is assembled, taking the assembled battery out of the glove box, sealing and forming the battery on a sealing machine, standing for 12 hours, and then testing the electrochemical performance of the battery.
Example 2:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, pre-blending and carbonizing: and uniformly mixing the powder with Polyethylene (PE) according to a ratio of 1:2, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 1.5h to obtain a pre-carbonized sample.
Step three, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
Step four, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
Example 3:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, pre-blending and carbonizing: uniformly mixing the powder with Polyethylene (PE) according to a ratio of 1:1, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 1.5h to obtain a pre-carbonized sample.
Step three, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
Step four, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
Example 4:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: uniformly mixing the powder with Polyethylene (PE) according to a ratio of 1:1, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 1.5h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
Compared with the blending carbonization-acid washing process in the embodiment 1, the embodiment has the advantage that the raw coal powder is acid washed before blending carbonization, so that the lamella spacing is largerLarge (d) 002 ) The performance improvement effect brought by the blending of the hard carbon material and the plastic is more obvious, and the reversible capacity of the hard carbon material is increased by 37.4mAh/g when the hard carbon material is used for a negative electrode of a sodium-ion battery.
Example 5:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: and uniformly mixing the powder with Polyethylene (PE) according to a ratio of 1:2, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 1.5h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The XRD pattern of the hard carbon material prepared in this example is shown in fig. 2, the crystallite parameters obtained by the preliminary calculation of the XRD pattern are shown in table 1, the specific morphology is shown in fig. 3, the rate performance and the charge-discharge curve are shown in fig. 4 and 5, and the graphite crystallite interlayer spacing d is shown in fig. 5 002 0.3836nm, transverse dimension L a 4.6429nm, longitudinal dimension L c 1.4042nm at 25mA g -1 346.3mAh g is obtained under the current density -1 The sodium storage capacity of (c).
Compared with the blending carbonization-acid washing process of example 2, the acid washing of the raw coal powder before blending carbonization in the example can obtain larger lamella spacing (d) 002 ) The performance improvement effect brought by the blending of the hard carbon material and the plastic is more obvious, and the reversible capacity of the hard carbon material is increased by 92.5mAh/g when the hard carbon material is used for a negative electrode of a sodium-ion battery.
Example 6:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: uniformly mixing the powder with Polyethylene (PE) according to a ratio of 1:1, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 1.5h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The XRD pattern of the hard carbon material prepared in this example is shown in fig. 6, the crystallite parameters obtained by the preliminary calculation of the XRD pattern are shown in table 1, the pore size distribution is shown in fig. 7, the rate capability and charge-discharge curve are shown in fig. 8 and 9, and the graphite crystallite interlayer spacing d is shown 002 0.3789nm, transverse dimension L a 4.8028nm, longitudinal dimension L c 1.5420nm at 25mA g -1 333.4mAh g is obtained under the current density -1 The sodium storage capacity of (c).
Compared with the blending carbonization-acid washing process of example 3, the acid washing of the raw coal powder before blending carbonization in the example can obtain larger lamella spacing (d) 002 ) The performance improvement effect brought by the blending of the hard carbon material and the plastic is more obvious, and the reversible capacity of the hard carbon material is increased by 147.6mAh/g when the hard carbon material is used for a negative electrode of a sodium-ion battery.
Example 7:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-carbonization: and heating the powder to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving the heat for 1.5h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The XRD pattern of the hard carbon material prepared in this example is shown in fig. 10, the crystallite parameters obtained by the preliminary calculation of the XRD pattern are shown in table 1, the specific morphology is shown in fig. 11, the rate performance and the charge-discharge curve are shown in fig. 12 and 13, and the graphite crystallite interlayer spacing d is shown in fig. 13 002 0.3846nm, transverse dimension L a 4.5970nm, longitudinal dimension L c 1.4489nm at 25mA g -1 320.5mAh g is obtained under the current density -1 The sodium storage capacity of (c).
Compared with example 5, the sodium storage capacity is 25.8mAh g lower -1 The introduction of polyethylene is shown to increase the sodium storage capacity of coal-based hard carbon.
Example 8:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-carbonization: and heating the powder to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving the heat for 1.5h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The XRD pattern of the hard carbon material prepared in this example is shown in fig. 14, the crystallite parameters obtained by the preliminary calculation of the XRD pattern are shown in table 1, the pore size distribution is shown in fig. 15, the rate capability and charge-discharge curve are shown in fig. 16 and 17, and the graphite crystallite interlayer spacing d is shown 002 0.3781nm, transverse dimension L a 4.8661nm, longitudinal dimension L c 1.5338nm at 25mA g -1 293.3mAh g is obtained at current density -1 The sodium storage capacity of (c).
Compared with example 6, the sodium storage capacity is 40.1mAh g lower -1 The introduction of polyethylene is shown to increase the sodium storage capacity of coal-based hard carbon. Meanwhile, the distribution rule of the pore diameter of the hard carbon material is changed, and partial 10-100 nm mesopores are converted into small mesopores of 1-10 nm.
Example 9:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: and uniformly mixing the powder with poly (p-xylylene glycol) (PET) according to a ratio of 2:1, heating to 700 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
Example 10:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: and uniformly mixing the powder with poly (p-xylylene glycol) (PET) according to a ratio of 2:1, heating to 700 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The XRD pattern of the hard carbon material prepared in this example is shown in fig. 18, the crystallite parameters obtained by the preliminary calculation of the XRD pattern are shown in table 1, the specific morphology is shown in fig. 19, the rate performance and the charge-discharge curve are shown in fig. 20 and 21, and the graphite crystallite interlayer spacing d is shown in fig. 21 002 0.3850nm, transverse dimension L a 4.1135nm, longitudinal dimension L c 1.3586nm at 25mA g -1 362.4mAh g is obtained under the current density -1 The sodium storage capacity of (c).
Example 11:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: and uniformly mixing the powder with poly (p-xylylene glycol) (PET) according to a ratio of 2:1, heating to 700 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The XRD pattern of the hard carbon material prepared in this example is shown in fig. 22, the crystallite parameters obtained by the preliminary calculation of the XRD pattern are shown in table 1, the pore size distribution is shown in fig. 23, the rate capability and charge-discharge curve are shown in fig. 24 and fig. 25, and the graphite crystallite interlayer spacing d is shown in fig. 25 002 0.3787nm, transverse dimension L a 4.7246nm, longitudinal dimension L c 1.6137nm at 25mA g -1 330.4mAh g is obtained under the current density -1 The sodium storage capacity of (c).
Example 12:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: and heating the powder to 700 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving the heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
Example 13:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-carbonization: and heating the powder to 700 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving the heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The multiplying power performance and the charging and discharging curve of the hard carbon material prepared in the embodiment are shown in fig. 26 and 27, and the graphite microcrystalline interlayer spacing d 002 0.3829nm, transverse dimension L a 5.0994nm, longitudinal dimension L c 1.4311nm at 25mA g -1 305.8mAh g is obtained under the current density -1 The sodium storage capacity of (c). Compared with example 10, the sodium storage capacity is 56.6mAh g -1 The introduction of poly (p-methyl glycol terephthalate) is shown to increase the sodium storage capacity of coal-based hard carbon.
Example 14:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw lignite to obtain 120-160-mesh powder.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-carbonization: and heating the powder to 700 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving the heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, heating to 1400 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
The pore size distribution of the hard carbon material prepared in this example is shown in FIG. 28, the rate capability is shown in FIG. 29, and the graphite crystallite interlayer spacing d is 002 0.3777nm, transverse dimension L a 4.6776nm, longitudinal dimension L c 1.5488nm at 25mA g -1 291.9mAh g is obtained under the current density -1 The sodium storage capacity of (c). Compared with example 11, the sodium storage capacity is 38.5mAh g lower -1 The introduction of poly (p-xylylene glycol) can increase the sodium storage capacity of the coal-based hard carbon. Meanwhile, the distribution rule of the pore diameter of the hard carbon material is changed, and partial 10-100 nm mesopores are converted into small mesopores of 1-10 nm.
Example 15:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening the raw coal of the lignite 2 to obtain powder of 120-160 meshes.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: uniformly mixing the powder with poly (p-xylylene glycol) (PET) according to a ratio of 2:1, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1000 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
Example 16:
the preparation method of the low-rank coal-based carbon material provided by the embodiment is carried out according to the following steps:
step one, grinding and selecting: and crushing and screening raw bituminous coal to obtain powder of 120-160 meshes.
Step two, acid washing: and (3) carrying out 5M hydrochloric acid pickling, water washing, 20% hydrofluoric acid pickling, water washing and drying on the powder material.
Step three, pre-blending and carbonizing: uniformly mixing the powder with poly (p-xylylene glycol) (PET) according to a ratio of 2:1, heating to 450 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, and preserving heat for 2h to obtain a pre-carbonized sample.
Step four, secondary carbonization: under the protection of argon atmosphere, heating the pre-carbonized product to 1000 ℃ at the speed of 5 ℃/min, then heating to 1200 ℃ at the speed of 2 ℃/min, and preserving heat for 2h to obtain the low-order coal-based hard carbon material.
The hard carbon material prepared in the embodiment is used as a negative electrode of a sodium ion battery and is subjected to electrochemical charge and discharge tests. See example 1 for a specific preparation and test procedure.
Table 1 relevant structural parameters and specific capacities for the preparation of negative electrode materials in the different examples
Note: lignite 1 is baorichile lignite, lignite 2 is lingquan lignite, and bituminous coal 1 is fugu bituminous coal.
Claims (9)
1. A preparation method of a waste plastic blending co-thermal conversion low-rank coal-based hard carbon material is characterized by comprising the following steps:
step one, raw material pretreatment:
crushing and screening raw coal to obtain raw coal powder with a target particle size;
step two, acid washing and deliming:
firstly, carrying out acid pickling and deashing treatment on raw coal powder by using hydrochloric acid, water, hydrofluoric acid and water in sequence, and then fully drying;
step three, mixing and carbonizing waste plastics:
uniformly mixing the acid-washed and dried raw coal powder with waste plastics, and pre-carbonizing in inert gas to obtain a pre-carbonized product, wherein the mass ratio of the raw coal powder to the waste plastics is 1: 0.01-2; the conditions for the precarbonization were as follows: heating to 450-700 ℃ according to the heating rate of 2-50 ℃/min, and preserving heat for 1-2 h;
step four, high-temperature carbonization:
grinding the pre-carbonized product uniformly, and then carrying out secondary carbonization in inert gas to obtain the low-order coal-based hard carbon material, wherein the conditions of the secondary carbonization are as follows: heating to 1000-1400 ℃ according to the heating rate of 2-5 ℃/min, and preserving heat for 1-2 h.
2. The method for preparing the waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1, wherein the raw coal is one or more of lignite No. one, lignite No. two and bituminous coal.
3. The preparation method of the waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1, wherein the target particle size of the coal is 120-400 mesh.
4. The method for preparing a waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1, wherein the waste plastic has a particle size of not more than 3 mm.
5. The method for preparing the waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1, wherein the concentration of the hydrochloric acid is 2-5M, the concentration of the hydrofluoric acid is 5-20 wt%, and the ratio of the volume of the acid to the mass of the raw coal powder is 5-20: 1.
6. The method for preparing the waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1, wherein the water is distilled water or deionized water, and the final effect of water washing is that the supernatant of the solution is neutral or weakly acidic.
7. The method for preparing the waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1 or 4, wherein the waste plastic is one or more of polyethylene, polypropylene, polystyrene and polyethylene terephthalate.
8. The method for preparing the waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1, wherein the inert gas is one or more of nitrogen and argon.
9. The preparation method of the waste plastic blending co-thermal conversion low-rank coal-based hard carbon material as claimed in claim 1, wherein the temperature rise rate of the pre-carbonization is 10-15 ℃/min.
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| CN116979064A (en) * | 2023-09-25 | 2023-10-31 | 宁德时代新能源科技股份有限公司 | Carbon material and preparation method thereof, negative electrode plate, secondary battery and power utilization device |
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